Method for the preparation of composite material in sandwich form

ABSTRACT

The object of the invention can be a method of manufacturing a product in the form of a sandwich comprising a core and outer layers. The outer layers may be composed of composite material comprising a fiber-reinforced polymeric matrix. The method uses an insert of heat-resistant material, for example silicone. The object of this invention can be to provide a method of manufacturing a sandwich that dissociates the choice of material of the core of the sandwich from the choice of the material of the outer layers.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a divisional of and claims priority under 35 U.S.C. § 120 to U.S. patent application Ser. No. 16/714,965, entitled “METHOD FOR THE PREPARATION OF COMPOSITE MATERIAL IN SANDWICH FORM,” by Gaetan MAO et al., filed Dec. 16, 2019, which claims priority under 35 U.S.C. § 119(a)-(d) to French Patent Application No. 1873207, entitled “METHOD FOR THE PREPARATION OF COMPOSITE MATERIAL IN SANDWICH FORM,” by Gaetan MAO et al., filed Dec. 18, 2018, both of which are assigned to the current assignee hereof and incorporated herein by reference in their entireties.

DETAILED DESCRIPTION

The invention relates to the field of products made of composite material or composite materials. Products made of composite materials means a product that may include a resin matrix consisting of a polymeric material, in particular, thermoplastic or thermosetting material. This matrix may be reinforced by a material that may have a melting point higher than the melting point of the polymeric material. FRP usually refers to “fiber reinforced plastic”.

Composite materials of the FRP type have good mechanical resistance with respect to the weight of the material. They also have very good resistance to corrosion. They have properties superior to those of the components taken separately. They allow in particular, in the field of automotive or aeronautics, lightening of parts traditionally made of steel. They also have good resistance to fatigue.

The reinforcements of the composite can be obtained in different ways: by the addition of mineral fibers dispersed in the matrix, by the use of a supporting structure made of steel or synthetic material, by the use of a reinforcing fiber fabric, by the use of non-wovens or mats or other products obtained by textile methods.

The fabric reinforcements may have a flat structure and may be composed of weft yarn and warp yarn intersecting and intertwining perpendicularly. Their manufacture may require the use of a separate spool by warp thread.

More recently, knitted reinforcements have been used. Knitted reinforcements can mean a product generally obtained from continuous yarn where the yarn forms mesh intertwined, arranged in successive rows. The production of a traditional knit requires only a spool of yarn for the yarn mesh.

The yarn may be of the monofilament or multifilament type. The multifilament may be a roving (i.e., set of parallel continuous filaments assembled without torsion), a spun yarn (i.e., a set of short staple fibers assembled with torsion). Yarn may also be an assembly of several yarns or filaments of different materials. This assembly can be done by twisting, wrapping. It is therefore possible to produce yarn comprising polymeric material and reinforcing material. For example, it is possible to assemble reinforcement yarn of the aramid, carbon, glass type, and thermoplastic yarn (i.e. polypropylene, polycarbonate, polyetherimide (PEI)). This type of yarn can then be called mixed yarn.

The knitting of this type of mixed yarn can make it possible to obtain a preform, containing both the reinforcement and the matrix. This preform is said to be “dry”, as opposed to the gummy and sticky resin pre-impregnated fabric commonly called “prepreg”.

It is also possible to produce products in the form of a sandwich that may include two outer layers, or skins, made of FRP type composite material and a central body, or core, of lighter material of the foam type or cellular honeycomb material. Thanks to their construction in the form of sandwich, these products can achieve, with equal weight, much better performances.

The impregnation of the skins and the binding of these to the core can influence the final properties of the sandwich composite. Good impregnation of the skins generally requires a consolidation method in several stages; which consumes time and resources. This is particularly the case when the finished product has a complex 3D shape.

The traditional methods for making a sandwich can generally include the following steps:

production of the outer layers using skins pre-impregnated with polymeric material;

juxtaposition of the outer layers on either side of a core, for example honeycomb or foam;

consolidation of the outer layers to ensure the melting of the polymeric material, while ensuring the connection of all layers to the core.

Depending on the thickness of the skins, it may be necessary to stack several folds. Several cycles of curing may then be necessary to ensure good consolidation of the fabric folds of each skin and ensure good adhesion between the skins and the core. With this type of manufacturing method, the core of the sandwich can be chosen specifically to resist the curing of the outer layers. In some cases, it has been found that it is impaired by putting under temperature and pressure. It has been observed, for example, that foam cores may sag or shrink during this treatment.

In addition, it also appeared that during curing, polymeric material could flow into the cells of the honeycomb.

Document EP 0 770 472 A1 outlines a method for manufacturing a composite material sandwich panel with a core formed of an open-cell structure and skins formed of fibers and resin. To avoid melting of the resin in the open cells of the core, the document provides for the interposition of a watertight membrane and a film of glue between the skins and the core. After closing the mold, a single thermal cycle makes it possible to polymerize the glue and then to inject the resin under pressure into the fibers and finally to polymerize the resin.

This method, however, has the disadvantage of requiring the use of several layers and in particular a watertight membrane. This increases the costs of the finished product.

Document EP 1 086 801 A1 outlines a method of manufacturing a sandwich panel by the resin injection technique, RTM. To avoid filling the honeycomb structure, this method requires the establishment in the mold of a film of an intumescent material and a barrier fabric on each of the faces of the core.

The method according to the invention uses an insert of heat-resistant material, to form the outer layers, instead of the core and the replacement of the insert by the core when the outer layers are consolidated. All that remains then is to perform heat treatment to bond the outer layers to the core.

According to a first embodiment, the method according to the invention may include the following steps:

Embodiment of outer layers or pre-impregnated skins, for example by knitting or weaving yarns that may include polymeric material and reinforcing material;

Juxtaposition in a mold, of an outer layer, an insert of heat-resistant material and a second outer layer;

Shaping of the skins by curing at a temperature and pressure that can allow consolidation and fusion of the polymeric material without reaching the melting point of the reinforcing material;

Removal of the insert and introduction of the core of the sandwich, for example, of foam or honeycomb, between the 2 preformed skins;

Curing of the assembly at a temperature to allow adhesion between the outer layers and the core of the sandwich.

According to another embodiment, the skins can be made from a textile of reinforcing material and the polymeric material can be provided by injection.

The method may then include the following steps:

Juxtaposition in a mold of a reinforcement fabric, an insert of material resistant to heat then another reinforcing fabric;

Resin injection;

Removal of the insert and introduction of the core of the sandwich, for example of foam or honeycomb, between the 2 preformed skins;

Curing the whole at a temperature allowing adhesion between the outer layers and the core of the sandwich.

The insert may be rigid or not. In particular, it can be silicone.

In some embodiments, it may expand at the temperature. This can allow increasing compression during consolidation.

The insert can provide a particular shape to the finished product, such as for example a beveled shape.

In some embodiments, an adhesive layer may be inserted between the sandwich body and the outer layers. This adhesive may be liquid glue, an adhesive film or a knitted preform comprising thermoplastic fibers.

The outer layers may be the same or different.

Advantageously, to obtain a good sandwich effect, the thickness of the core can be generally at least about 2 mm and not greater than about 50 mm, preferably at least about 3 mm and not greater than about 40 mm, and more preferably at least about 5 mm and not greater than about 25 mm, and the thickness of the skin can be at least about 0.2 mm and not greater than about 5 mm, preferably at least about 0.4 mm and not greater than about 2 mm, and more preferably at least about 0.5 mm and not greater than about 1 mm.

The object of this invention can be to provide an alternative method of manufacturing a sandwich, in particular to provide a manufacturing method that dissociates the choice of material of the body of the sandwich and the choice of the material of the outer layers.

Polymeric material may include thermoplastic materials such as, for example, polycarbonate (PC), polyetherimide (PEI), polypropylene (PP), poly(ethylene terephthalate) (PET), polyether ether ketone (PEEK), or thermosetting materials such as for example epoxy, cyanate ester, phenolic resin, polyester.

Reinforcing material may include synthetic materials, such as para-aramid, polypropylene, natural materials, such as linen, inorganic materials, such as glass, quartz, carbon, basalt, metal.

The method according to the invention has proven particularly advantageous because it can make it possible to dissociate the choice of the type of core of the sandwich from the choice of the transformation method. The method according to the invention can make it possible to achieve good impregnation of the outer skins.

Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, skilled artisans will appreciate that those aspects and embodiments are only illustrative and do not limit the scope of the present invention. Embodiments may be in accordance with any one or more of the embodiments as listed below.

Embodiment 1. A method of manufacturing a sandwich-shaped composite material product wherein the sandwich-shaped composite material product comprises two outer layers and a core, the outer layers having a matrix of fiber-reinforced polymeric material, the polymeric material having a melting point below the melting point of the material constituting the fibers; wherein the method being characterized in that it uses an insert consisting of material having a melting point higher than the melting point of the polymeric material, on which the outer layers are consolidated; and wherein this insert is subsequently replaced by the core of the sandwich, the assembly then undergoing a consolidation treatment for bonding the outer layers to the core.

Embodiment 2. The method according to embodiment 1, characterized in that it comprises the following steps: production of preforms composed of fiber-reinforced polymeric material intended to become the outer layers of the sandwich, juxtaposition, in a mold, of a first preform, of the insert, and of a second preform, consolidation of the preforms to obtain the outer layers, by heating and pressurizing, to reach the temperature of the melting point of the polymeric material, without reaching the temperature of the melting point of the reinforcing material or the material of the insert, removal of the insert, separation of the outer layers and insertion of the core of the sandwich, heat treatment to adhere the outer layers to the core, cooling of the product thus obtained.

Embodiment 3. The method according to embodiment 2, characterized in that the preforms are made using pre-impregnated polymer resin fabrics.

Embodiment 4. The method according to embodiment 2, characterized in that the preforms are made by knitting a yarn comprising the reinforcing material and the polymeric material.

Embodiment 5. The method according to embodiment 2, characterized in that a peel cost is added between the preforms, at the places intended to form a zone without a core.

Embodiment 6. The method according to embodiment 1, characterized in that it comprises the following steps: juxtaposition, in a mold, of a fabric or knit made of reinforcing material, the insert, and a second fabric or knit made of reinforcing material; injection of a resin of polymeric material under pressure and temperature; removal of the insert and insertion of the core of the sandwich; consolidation curing to adhere the outer layers to the core of the sandwich; cooling of the product thus obtained.

Embodiment 7. The method according to embodiment 1, characterized in that the insert is made of silicone.

Embodiment 8. The method according to embodiment 1, characterized in that the reinforcing material is chosen from glass, carbon and aramid fibers.

Embodiment 9. The method according to embodiment 1, characterized in that the polymeric material is of the thermoplastic type, in particular chosen from polycarbonate (PC), polyetherimide (PEI), polypropylene (PP), poly(ethylene terephthalate) (PET), polyether ether ketone (PEEK).

Embodiment 10. The method according to embodiment 1, characterized in that the polymeric material is of the thermosetting type, in particular chosen from epoxy, cyanate ester, phenolic resins and polyester.

Embodiment 11. The method according to embodiment 1, characterized in that the core of the sandwich consists of cellular honeycomb material.

Embodiment 12. The method according to embodiment 1, characterized in that the thickness of the core is at least about 2 mm and not greater than about 50 mm.

Embodiment 13. The method according to embodiment 1, characterized in that the thickness of each of the outer layers is at least about 0.2 mm and not greater than about 5 mm.

The following examples illustrate the invention in a non-limiting manner.

EXAMPLES Example 1

Several “prepreg” cyanate ester impregnated carbon fiber fabrics are draped in a steel mold to form the first skin of the sandwich.

A rigid insert (for example a Teflon® block of a few millimeters) is deposited on the fabrics.

The second skin of the sandwich is made by draping several “prepreg” fabrics on the rigid insert.

Teflon-coated peel ply (PTFE-coated glass fibers) is placed at the junction between the two skins. The junction is the area where the skins join to cover the field of the core.

The mold is closed by a flexible counter-mold.

The skins are consolidated by heat treatment under vacuum at about 180-220° C. for a few hours.

The assembly is allowed to cool and the insert is removed.

A high-temperature-resistant glue is applied to each of the faces intended to be in contact with the core.

A polyimide foam-type core (approximate density of 50 kg/m3) is introduced in place of the insert.

The entire sandwich is then subjected to a final consolidation treatment, under vacuum at a temperature of about 90-120° C., so as to ensure good adhesion of the skins and the core.

Example 2

The first skin is formed by a stack of several non-impregnated reinforcing fabrics, of carbon fibers, deposited in a steel mold.

A soft insert (silicone plate a few millimeters thick) is deposited on the fabric.

The second skin is formed by a fabric of the same type deposited on the insert.

The mold is closed by the steel counter mold.

Cyanate ester resin is injected by a known RTM-type method, at a temperature between 80 and 120° C. under a pressure of 10 to 15 bar.

The heat treatment is prolonged for 4 hours.

The mold is allowed to cool, then the insert is removed and the skins are separated by removing the peel ply.

A very thin layer of cyanate ester resin is added to the skins (on the faces intended to come into contact with the honeycomb).

A honeycomb core is introduced between the two skins, in place of the insert, to form a sandwich.

The entire sandwich is subjected to heat treatment (180-200° C.), under vacuum, for 4 hours so as to bond the skins and the core.

Example 3

A knit is made using a mixed yarn comprising glass fibers and thermoplastic fibers.

This knit is deposited in a steel mold to form the first skin.

An insert of material expandable under the effect of temperature is deposited on the knit.

A second knit of the same type is deposited on the insert to form the second skin.

Teflon-coated peel ply (PTFE-coated glass fibers) is placed at the junction between the two skins. The junction is the area where the two skins join to cover the field of the core.

Teflon-coated peel ply is placed at the junction between the two skins.

The mold is closed by a steel counter mold.

The skins are consolidated by heat treatment at 200-250° C., under a pressure of 3 to 10 bar for a few dozen minutes.

The mold is allowed to cool, then the insert is removed and the skins are separated by removing the peel ply.

A knit preform of a thermoplastic yarn is deposited on either side of a honeycomb core, so as to form a connecting layer between the core and the skins of the sandwich.

The honeycomb core and the knit preforms are introduced between the two skins, in place of the insert, to form a sandwich.

The entire sandwich is subjected to heat treatment (200-250° C.), under vacuum, for a few hours, so as to bond the skins and the core.

Example 4

A knit is made using a mixed yarn comprising glass fibers and thermoplastic fibers.

This knit is deposited in a steel mold to form the first skin.

A rigid insert of material expandable under the effect of temperature is deposited on the knit.

A second knit of the same type is deposited on the insert to form the second skin.

Teflon-coated peel ply is placed at the junction between the two skins.

The mold is closed by a steel counter mold.

The skins are consolidated by a heat treatment at 200-250° C., under a pressure of 3 to 10 bar for few dozen minutes.

The mold is allowed to cool, then the insert is removed and the skins are separated by removing the peel ply.

An expanded epoxy foam core is injected between the two skins, in place of the insert, to form a sandwich.

The whole sandwich is subjected to heat treatment (65-120° C.), under vacuum, for a few hours so as to bind the skins and the core.

Example 5

A knit is made using a mixed yarn comprising glass fibers and thermoplastic fibers.

A first knit is draped over a silicone bladder and the assembly is deposited in a first steel mold for the consolidation of the outer skin. The mold is closed and a vacuum is drawn. The mold is pressurized (3 to 10 bar) and heated rapidly by induction heating to a temperature of 200 to 250° C. The temperature is maintained for a few minutes. After cooling, the bladder is removed and a first skin is thus produced.

A second skin (inner skin) is made in the same way as the first in a second mold.

In the tooling used to consolidate the outer skin, the following is deposited successively: the external skin previously consolidated, an epoxy or liquid form glue film, a honeycomb structure, the previously consolidated internal skin of the final composite product.

The silicone bladder used to consolidate the inner skin is put in place and the mold is closed. A vacuum is drawn to the maximum and the assembly is heated to a temperature of 65-120° C. for a few hours (oven heating method) so as to bond the skins and the core. 

What is claimed is:
 1. A method of manufacturing a sandwich-shaped composite material product wherein the sandwich-shaped composite material product comprises two outer layers and a core, the outer layers having a matrix of fiber-reinforced polymeric material, the polymeric material having a melting point below the melting point of the material constituting the fibers; wherein the method being is characterized in that it uses an insert consisting of material having a melting point higher than the melting point of the polymeric material, on which the outer layers are consolidated; and wherein this insert is subsequently replaced by the core of the sandwich-shaped composite material product to form an assembly, the assembly then undergoing a consolidation treatment for bonding the outer layers to the core, wherein the method is further characterized in that it comprises the following steps: juxtaposition, in a mold, of a fabric or knit made of reinforcing material, the insert, and a second fabric or knit made of reinforcing material; injection of a resin of polymeric material under pressure and temperature; removal of the insert and insertion of the core of the sandwich; consolidation curing to adhere the outer layers to the core of the sandwich; cooling of the product thus obtained.
 2. The method according to claim 1, characterized in that the insert is made of silicone.
 3. The method according to claim 1, characterized in that the reinforcing material is chosen from glass, carbon and aramid fibers.
 4. The method according to claim 1, characterized in that the polymeric material is of the thermoplastic type chosen from polycarbonate (PC), polyetherimide (PEI), polypropylene (PP), poly(ethylene terephthalate) (PET), and polyether ether ketone (PEEK).
 5. The method according to claim 1, characterized in that the polymeric material is of the thermosetting type, chosen from epoxy, cyanate ester, phenolic resins and polyester.
 6. The method according to claim 1, characterized in that the core of the sandwich-shaped composite material product consists of cellular honeycomb material.
 7. The method according to claim 1, characterized in that the thickness of the core is at least about 2 mm and not greater than about 50 mm.
 8. The method according to claim 1, characterized in that the thickness of each of the outer layers is at least about 0.2 mm and not greater than about 5 mm. 